Process for breaking water-in-oil emulsions



l M733@ Feb. 15, 1927 C. CS AVERILL I PROCESS FOR BREAKINGI WATER-IN- OIL EMULSION Filed Nov. 21. `1925 Ar ro @Mem a quiescent state.

Patented Feb. 15, 1927.

n s'rAss PATENT. OFFICE.

CHARLES C. AVERILL, OF HOUSTON, TEXAS, ASSIGNOE T0 WM. S. BABNICKEL & COM- PANY, OF WEBSTER GROVES, MISSOURL A CORPORATION OF MISSOURI.

PROCESS FOR BREAKING WATER-IN-OIL EMULSIONS.

Application filed November 21, 192,5. Serial No. 70,538.

This invention relates to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the Water.

Petroleum emulsions are of the Water-inoil type, and consist of oil constituting the continuous phase of the emulsions, droplets of Waterv distributed throughout the body of oil and constituting the dispersed phase of the emulsion, and tilms ot matter that encase the droplets of oil.

Emulsions of the kind above referred to which require treatment in the oil fields may be Vroughly dividedA into three separate and distinct classes:

1st. Temporary emulsions, which usually break when they are subjected to a moderate temperature and then allowed to remain in 2nd. Emulsions which are sufficiently permanent to be unaffected by moderate heat alone, but which can be resolved or broken by the processes noW generally used in the oil fields for treating petroleumlemulsions.

such as the chemical process, the boiling pit process, the electrical process and the centritugal process; and

3rd. Obstinate or stubborn emulsions which ordinarily cannot be broken citer-,tively or economically by one or the other ot. the conventional processes above referred to.

,The obstinate emulsions which make up this third class comprise tank bottoms or sediment that collects or builds up on the bottoms of oil storage tanks and which consist of oil mined with colloidal sand, parailin Wax and other obnoxious solids in such pro portions that the conventional processes used for breaking oil emulsions are either incapable of breaking them lor are so expensive that they cannot be used commercially; pit oils which are obtained from earthen pits in which oil is stored when steel or wooden storage tanks are not available and which contain relatively great quantities of solids that stabilize the emulsion; storage oils which consist ot oil emulsions that have been stored for long periods and which do not respond to treat-ment with conventional treating processes, due "to the fact that age has made the .emulsifying films practically impervious to the passage of the droplets of Water or brine which said films encascp and freak emulsions which consist of freshly produced emulsions that contain enermous amounts of sand and other emulsitying.,r material.

My invention relates to the treatment ot stubborn or obstinate emulsions ot the kind above' referred to, and the. object of the invention is to provide a process that will not. only effectively break such stubborn emulsions, but which is inexpensive and capable ot' being practisedor carried out in an apparatus ot' simple design that can be. easily obtained in localities where, such stubborn emulsions exist or are produced. 'lhis characteristic of being able to be practised with an inexpensive apparatus ot' simple design makes myl process commercially feasible for use in oil fields and tank farms, because it is only at infrequent intervals that sediment is removed from the bottoms ot oil storage tanks and only relatively small quantities ot' tank bottoms are obtainable in any partienlar locality; it is only in rare cases that ircak emulsions" are produced and it only in rare cases that oil gushes from a producing well in such quantities that earthen?` pits have to be resorted to for storing theoil.

Brietiy stated, my process consists in thoroughly mixing with a stubborn or obstinate emulsion of the kind above referred to, a quantity ot water at least equal in volume. tothe. amount ot emulsion and sometimes equal in volmne, to three or tour times the amount ot' the emulsion, and thereafter subjecting the emulsion to the action ot a chemical demulsi't'ying agent. The water that is added to the cnnilsion may be hard water, sott water, salty water or alkaline water, and heat is preferably employed to assist the treating agent or demulsifyinfr agent to break the emulsion. Any suitable means can be employed to mix the Water with the emulsion, but in most instances an emulsifying valve will 'be used to mix the water With the emulsion and sutiicient Water will be added so that the original emulsion cannot takeup all this Water as dispersed Water, thus causingr the excess Water to tend to produce a distinctly di'erent type of emulsion, to wit, an oil-in-water emulsion, in which the excess Water constitutes the continuous phase and the oil of the original emulsion, plus the extra Water which was dispersed into it, constitutes the dispersed phase. After the Water has been added to the emulsion the temperature of said mix ture is preferably raised and a chemical demulsifying agent is added to same so as to cause the emulsion to separate into its component parts, when it is allowed to stand in a quiescent state, the temperature to which the mixture is raised varying from 160 F. to 240 F.

The novelty of the above descr-ibed process consists in the addition ot excessive quantities of Water to the emulsion prior to the chemical treatment as I have demonstrated that stubborn emulsions which could not be broken by a demulsifying agent 'and the addition of a moderate amount of water would respond to treatment and would break and separate into a clearly defined layer ot' oil and a layer of Water or brine, when subjected to the treatment above described.

One example thatV I will cite of an emulsion which responded to treatment by 'Y my processbut which 'failed to break when subjected to treatment by'the conventional chemical treating process is an emulsion consisting of tank bottoms obtained from oil storage tanks at Texas City, Texas. Ex-

haustive tests made with this emulsion' showed` that the. emulsion could not be broken with heat alone, or with heat and a moderate amount of Water. Even when the emulsion was conditioned by heating it, adding armoderate amount of Water and treating it with a chemical treating agent or demulsifying agent at a ratio 'of approxi- A mately 1 bbl. of .treating agent to 2000 bbls.

of emulsion, the4 emulsion failed to break. When, however, this same emulsion Vwas conditioned according to my invention and also' chemically treated with the same demulsitying agent at a ratio of approximately l bbl. of treating agent to 8,000 bbls. of emulsion, the emulsion broke and acceptable pipe line oil Was recovered from same.

Conditioning or treatment of a stubbornl emulsion, as above described, not only materially reduces the quantity of chemical treating agent or demulsifying agent that is required to produce a break, but it also permits the use Vof chemical demulsifying agents which are too Weak to be used economically in instances where the emulsion is not conditioned or subjected to treatment Vin ac cordance with my invention. For example, I can eil'ectively breaka stubborn emulsion by converting it into an oil-in-water emulsion, as above described, and treating it with a chemical demulsifying agent consisting of hydrophile emulsifying agents, such as unmodified glue, starch, gelatine, gum acaciaand saponin capable of producing an oilm-water emulsion. I have also found that such a conditioned emulslon can be broken when subjected to treatment with treating agents consisting of substanceswhich of themselves are not hydrophile emulsifying agents, but which, in combination with the organic acidic material of the petroleum, such as naphthenic acids, tend to produce water-soluble salts, having the ability to emulsify oil in water. These substances in clude oilsoluble or water-soluble n'iaterinl having basic characteristics, such as caustic soda, soda ash, potash, sodium bicarbonate, ammonium hydrate, borax, sodium phosphate, aniline and pyridine.

Figure-1 ot the drawings is a diagrammatic, side elevational yiew ot an apparatus that can be used for practicing my process and Figure 2 is an enlarged side elevational view of the emulsifying device.4

Referring to'the drawings, A, designates` a tank that is adapted tohold the emulsion, after the water has been added to same, B designates a pump whose intake is connected with an emulsion pipe C that leads from a source of supply and also With'a'water pipe D that leads from a source of supply, such, for example, as a water pit E, F designates a heating device in the line G through which the mixture ot' emulsion and water is introduced into the tank A, H designates anagent which is introduced into the emulsion flowing into the tank A, .and J designates a 'storage tank into-Which the clear or substantially clear oil is drawn from the tank A.

The emulsifying deviceH can consist of any suitable device or apparatus that will subject the emulsionfand' Water. to an emulsifying operation and cause the water to be thoroughly mixed with the emulsion. In the apparatus h ereinshown said emulsifying device H consists ot' a valve of the kind illustrated in Figure 2, which is so constructed or adjusted that the passage of the emulsion and Water through said valve subjects said emulsion and water to a vigorous agitation, said valve comprising a tapered valve element l arranged with its peripheral edge spacedslightly away from a tapered valve seat 2 when the mixture is passing through the-valve and havin its stem A3 pivotally connected to a weig ted lever emulsion will be added to the emulsion. In all cases sucient water is added to the emulsion, so that the emulsion cannot take up all of this water as dispersed. water, therebycausing the excess Water to tend to produceA an oil-in-water emulsion, as previously described. The mixture produced by the emulsionan'd the Water drawn into the pump B is subjected to a temperature varying from 160 F. to 240 F., in assing` through the heating'device F. if desired the container I can' be equipped with a valve 6 that can be closed so as to cut od communie cation between said container and the line Gthrougli which the water and emulsion enter the tank A. Normally the valve 6 is open so as to cause a chemical treating agent or demulsifying agent to pass from the container I into the line G, thus subjecting the emulsion to the action of a chemical demulsifylng agent, as is'the conventional chemical process for treating waterin-oi1 emulsions. It is immaterial, whether the chemical demulsifying agent is introduced into the emulsion before or after the emulsion passes through the emulsiiying device H, but in most instances thecontainer l will be arranged in advance of said emulsifying device, so as to cause the'device H to produce emulsication and also thoroughly mix the chemical demulsiying agent with the emulsion.

Having thus described my invention,

what i claim as new and desire te secure by Letters Patent is: j

l. A. process for breaking tratarn-eil emulsions, characterized by adding to the emulsion an amount of water at east equal in volume to the quantity of the emulsion, subjecting said mixture to an emulsifying operation and also-subjecting said mixture.

to the action of a chemical demulsiiying agent which tends to cause the emulsion to break and separate into its component parts.

2. A process 'for breaking Water-in-oil emulsions characterized by adding to the emulsion an amount of Water at least equalin volume to the`quantity of the emulsion and at least sufficient to be in excessf of the amount of water which the emulsion canV in volume to the quantity of the emulsion,`

subjecting' said mixture to an emulsiying operation, heating the mixture andl also subjecting the mixture to the action of a chemical demulsifying agent.

CHARLES cgAVEnILL. 

